STABILISATEURS A BASE DE MERCAPTO-ETAIN ET D'UN DIESTER D'ACIDE DICARBOXYLIQUE INSATURE, POUR POLYMERES ORGANIQUES HALOGENES

STABILIZERS FOR HALOGEN-CONTAINING ORGANIC POLYMERS COMPRISING AN ORGANOTIN MERCAPTIDE AND A DIESTER OF AN UNSATURATED DICARBOXYLIC ACID

Abrégé anglais

ABSTRACT
A composition is disclosed which comprises an
organotin mercaptide and/or an organotin sulfide with
a dialkyl ester of an ethylenically unsaturated
dicarboxylic acid. The composition is effective for
stabilizing rigid halogen-containing organic polymers
against deteriorative effects of heat, light and
weathering.

Revendications

We claim:
1. A composition capable of stabilizing halogen-containing
organic polymers against the deteriorative effects of heat, light
ant weathering, said composition comprising the product produced
by combining:
A. an organotin compound or mixture of organotin compounds
selected from the group consisting of organotin sulfides,
organotin mercaptides and mixtures thereof; and
B. in an amount sufficient to synergize the stabilization of
the halogen-containing organic polymer but insufficient
to plasticize said polymer, a diester of an ethylenically
unsaturated dicarboxylic acid having one carboxyl group
on each carbon atom of the ethenylene group and 1 to 10
carbon atoms in the alcohol portion of the ester moieties.
2. The composition of claim 1 wherein the organotin compound is
an organotin sulfide or mixture of organotin sulfides having the
formula:
(I) <IMG>
(II) R2Sn=S
where R is at each independent occurrence selected from alkyl,
alkenyl, cycloalkyl, cycloalkenyl,
<IMG>
43

wherein R8 is at each independent occurrence selected from alkyl,
alkenyl, cycloalkyl or cycloalkenyl;
R9 is at each independent occurrence selected from C1 to
C4 alkylene;
R12 is at each independent occurrence selected from -H
or a monovalent C1 to C20 hydrocarbon radical; and
R13 and R14 are at each independent occurrence selected
from C1 to C20 alkyl or C1 to C20 alkoxy.
3. The composition of claim 1 wherein the organotin compound is
an organotin mercaptide or mixture of organotin mercaptides
having the formulae;
(III) <IMG>

(IV) Rn-Sn-Xp or
(V)
<IMG> wherein
X is at each independent occurrence selected from
<IMG> or
<IMG> with the proviso that; (1) at least
one X in formulas III and IV is -SR2 and (2) in formula
V at least one X is -SR2 or at least one Y is -S-R3-E
<IMG>
Y is at each independent occurrence selected from
<IMG>
E is at each independent occurrence selected from oxygen or
sulfur:
R is at each independent occurrence selected from alkyl, alkenyl,
cycloalkyl, cycloalkenyl,
<IMG>
44

R2 is at each independent occurrence selected from alkyl, alkenyl,
<IMG>
cycloalkyl, cycloalkenyl,
R3 is at each independent occurrence selected from alkylene of at
least 2 carbon atoms, alkenylene of at least 2 carbon atoms,
cycloalkylene, or cycloalkenylene,
R4 is at each independent occurrence selected from alkylene,
alkenylene, cycloalkylene, or cycloalkenylene;
R6 is at each independent occurrence selected from a carbon-carbon
bond, or R4;
R7 is at each independent occurrence selected from -H or R8;
R8 is at each independent occurrence selected from alkyl,
alkenyl, cycloalkyl, or cycloalkenyl;
R9 is at each independent occurrence selected from C1 to C4
alkylene;
R12 is at each independent occurrence selected from -H or a
monovalent C1 to C20 hydrocarbon radical;
R13 and R14 are at each independent occurrence selected from C1 to
C20 alkyl or C1 to C20 alkoxy;
at each independent occurrence n-1 or 2 and p=4-n;
at each independent occurrence a = 1 or 2; b = 2-a;
c = 1 or 2; d = 3-c; and q = 0 or an integer from 1 to 4
inclusive; and
v is at each independent occurrence selected from an integer
from 1 to 8 inclusive.
4. The composition of claim 1 wherein the diester of an
ethylenically unsaturated dicarboxylic acid is a diester or
mixture of diesters having the formula:

<IMG>
(VI)
where R100 and R103 are the same or different and are at each
independent occurrence alkyl, alkenyl, cycloalkyl, cycloalkenyl,
or a multivalent hydrocarbyl or hydroxyl-substituted hydrocarbyl
group;
R101 is at each independent occurrence a carbon-oxygen bond,
alkylene or alkenylene with the proviso that the total carbon
atoms in each of R100 and R103 plus R101 is from 1 to 10;
R102 is at each independent occurrence selected from hydrogen,
alkyl and alkylene; and
t is an integer of from 1 to about 20.
5. The composition of claim 4 wherein the diester is a dialkyl
maleate.
6. The composition of claim 5 wherein the dialkyl maleate is
dibutyl maleate.
7. The composition of claim 1 wherein the molar ratio of the
organotin compound of component A to the diester of component B is
from about 2/1 to about 1/8.
8. The composition according to claim 1 which further comprises
in an amount sufficient to synergize the stabilization of the
halogen-containing organic polymer, an organotin carboxylate or
mixture of organotin carboxylates.
9. The composition of claim 8 wherein the organotin carboxylate
or mixture of organotin carboxylates has the formula;
(VII)
<IMG>
<IMG>
(VIII) or
<IMG>
(IX)
46

wherein R, n, p, a, b, c, d and q are as previously defined in
claim 3;
<IMG>
Z is
<IMG> <IMG>
A is or
R3, R4, R7 and R8 are as defined in claim 3 ; and
r=0 or an integer.
10. The composition of claim 9 wherein the organotin carboxylate
is an alkyltin alkyl maleate.
11. The composition of claim 10 wherein the alkyltin alkyl
maleate is dibutyltin bis(butyl maleate).
12. The composition of claim 8 wherein the molar ratio of the
organotin compounds from to diesters is about 2/1 to about 1/8.
13. A composition comprising a halogen-containing organic polymer
and, in an amount sufficient to stabilize said polymer against the
deteriorative effects of heat, light and weathering, a stabilizer
composition according to claim 1.
14. A composition according to claim 13 which contains about 1.0%
to about 5.0% of the stabilizer composition, the percentages being
by weight based on the weight of the halogen-containing organic
polymer.
15. A composition comprising a halogen-containing organic polymer
and, in an amount sufficient to stabilize said polymer against the
deteriorative effects of heat, light and weathering, a stabilizer
composition according to claim 8.
16. A composition according to claim 15 which contains about 1.0%
to about 5.0% of the stabilizer composition, the percentages being
by weight based on the weight of the halogen-containing organic
polymer.
47

17. A composition capable of stabilizing halogen-containing
organic polymers against the deteriorative effects of heat, light
and weathering, said composition comprising the product produced
by combining:
A. an organotin compound or mixture of organotin compounds
selected from the group consisting of organotin sulfides,
organotin mercaptides, organotin carboxylates, and mixtures
thereof; and
B. in an amount sufficient to synergize the stabilization of
the halogen-containing organic polymer but insufficient
to plasticize said polymer, an essentially non-lubricating
diester of a C1-C10 alcohol and an ethylenically unsaturated
dicarboxylic acid having one carboxyl group on each carbon
atom of the ethenylene group said diester having the
formula:
<IMG>
where:
R200 and R203 each have from 1 to 10 carbon atoms and
are at each independent occurrence selected from alkyl,
alkenyl, cycloalkyl, cycloalkenyl, multivalent hydrocarbyl
group having a valence equal to z', multivalent hydroxyl
substituted hydrocarbyl group having a valence equal to z',
and <IMG>;
R201 is at each independent occurrence selected from alkylene,
alkenylene, cycloalkylene, cycloalkenylene, a multivalent
hydrocarbyl group and multivalent hydroxyl-substituted
hydrocarbyl group;
R202 is at each independent occurrence selected from hydrogen,
alkyl and alkylene;
R204 is at each independent occurrence selected from hydrogen and
alkyl;
48

Z200 is at each independent occurrence selected from -O-,<IMG>
<IMG> , and -S-;
t' is zero or an integer from 1 to about 20;
x' is zero or an integer from 1 to about 20 with the proviso that
if x =0 or t'=0 then R200 is <IMG>
y' is an integer from 1 to 10; and
z' is an integer from 1 to 4.
18. The composition of claim 17 wherein the organotin compound is
an organotin sulfide or mixture of organotin sulfides having the
formulae.
(I) <IMG>
(II) R2Sn=S
where R is at each independent occurrence selected from alkyl,
alkenyl, cycloalkyl, cycloalkenyl,
<IMG>
49

wherein R8 is at each independent occurrence selected from alkyl,
alkenyl, cycloalkyl or cycloalkenyl;
R9 is at each independent occurrence selected from C1 to
C4 alkylene;
R12 is at each independent occurrence selected from -H
or a monovalent C1 to C20 hydrocarbon radical; and
R13 and R14 are at each independent occurrence selected
from C1 to C20 alkyl or C1 to C20 alkoxy.
19. The composition of claim 17 wherein the organotin compound is
an organotin mercaptide or mixture of organotin mercaptides having
the formulae:
(III) <IMG>
49a

(IV) <IMG> or
(V)
<IMG> wherein
X is at each independent occurrence selected from
<IMG>
or
<IMG> with the proviso that: (1) at least
one X in formulas III and IV is -SR2 and (2) in formula
V at least one X is -SR2 or at least one Y is -S-R3-E
<IMG>
Y is at each independent occurrence selected from
<IMG>
E is at each independent occurrence selected from oxygen or
sulfur;
R is at each independent occurrence selected from alkyl, alkenyl,
cycloalkyl, cycloalkenyl,
<IMG>

R2 is at each independent occurrence selected from alkyl, alkenyl,
<IMG>
cycloalkyl, cycloalkenyl,
<IMG>
R3 is at each independent occurrence selected from alkylene of at
least 2 carbon atoms, alkenylene of at least 2 carbon atoms,
cycloalkylene, or cycloalkenylene;
R4 is at each independent occurrence selected from alkylene,
alkenylene, cycloalkylene, or cycloalkenylene;
R6 is at each independent occurrence selected from a carbon-carbon
bond, or R4;
R7 is at each independent occurrence selected from -H or R8;
R8 is at each independent occurrence selected from alkyl,
alkenyl, cycloalkyl, or cycloalkenyl;
R9 is at each independent occurrence selected from C1 to C4
alkylene;
R12 is at each independent occurrence selected from -H or a
monovalent C1 to C20 hydrocarbon radical;
R13 and R14 are at each independent occurrence selected from C1 to
C20 alkyl or C1 to C20 alkoxy;
at each independent occurrence n=1 or 2 and p=4-n;
at each independent occurrence a = 1 or 2; b = 2-a;
c = 1 or 2; d = 3-c; and q = 0 or an integer from 1 to 4
inclusive; and
v is at each independent occurrence selected from an integer
from 1 to 8 inclusive.
20. The composition of claim 17 wherein the organotin carboxylate
has the formulae:

(VII) Rn-Sn-Zp
(VIII) <IMG> or
(IX)
<IMG>
where:
R is at each independent occurrence selected from alkyl, alkenyl,
cycloalkyl, cycloalkenyl,
<IMG>
R8 is at each independent occurrence selected from alkyl,
alkenyl, cycloalkyl, or cycloalkenyl;
R9 is at each independent occurrence selected from C1 to C4
alkylene;
R12 is at each independent occurrence selected from -H or a
monovalent C1 to C20 hydrocarbon radical;
R13 and R14 are at each independent occurrence selected from C1 to
C20 alkyl or C1 to C20 alkoxy;
Z is <IMG> or <IMG>
A is <IMG> or <IMG>
R3 is at each independent occurrence selected from alkylene of at
least 2 carbon atoms, alkenylene of at least 2 carbon atoms,
cycloalkylene, or cycloalkenylene;

R4 is at each independent occurrence selected from alkylene,
alkenylene, cycloalkylene, or cycloalkenylene;
R7 is at each independent occurrence selected from -H or R8;
at each independent occurrence n=1 or 2 and p=4-n;
at each independent occurrence a = 1 or 2; b = 2-a;
c = 1 or 2; d = 3-c; and q = 0 or an integer from 1 to 4
inclusive; and
r=0 or an integer.
21. The composition of claim 17 wherein the diester is
diethyleneglycol bis(butyl maleate).
22. A composition of claim 17 wherein the diester is triethylene
glycol bis(butyl maleate).
23. The composition of claim 17 wherein the diester is
tetraethylene glycol bis(butyl maleate).
24. The composition according to claim 17 wherein the diester is
poly(diethyleneglycol maleate) bis(methyl maleate).
25. The composition of claim 17 wherein the molar ratio of the
organotin compound of component A to the diester of component B
is from about 2/1 to about 1/8.
26. A composition comprising a halogen-containing organic polymer
and, in an amount sufficient to stabilize said polymer against
the deteriorative effects of heat, light and weathering, a
stabilizer composition comprising the product produced by
combining:
A. an organotin compound or mixture of organotin compounds
selected from the group consisting of organotin sulfides,
organotin mercaptides, organotin carboxylates and mixtures
thereof; and
B. in an amount sufficient to synergize the stabilization of
the halogen-containing organic polymer but insufficient
to plasticize said polymer, an essentially non-lubricating
diester of C1 to C10 alcohol and an ethylenically unsatura-
ted dicarboxylic acid having one carboxyl group on each
carbon atom of the ethenylene group, said diester having
the formula:
53

<IMG>
where:
R200 and R203 each have from 1 to 10 carbon atoms and
are at each independent occurrence selected from alkyl,
alkenyl, cycloalkyl, cycloalkenyl, multivalent hydrocarbyl
group having a valence equal to z', multivalent hydroxyl
substituted hydrocarbyl group having a valence equal to z',
and <IMG>
R201 is at each independent occurrence selected from alkylene,
alkenylene, cycloalkylene, cycloalkenylene, a multivalent
hydrocarbyl group and multivalent hydroxyl-substituted
hydrocarbyl group;
R202 is at each independent occurrence selected from hydrogen,
alkyl and alkylene;
R204 is at each independent occurrence selected from hydrogen and
alkyl;
Z200 is at each independent occurrence selected from -O-, <IMG>
<IMG> and -S-;
t' is zero or an integer from 1 to about 20;
x' is zero or an integer from 1 to about 20 with the proviso that
if x'=0 or t'=0 then R200 is <IMG>
y' is an integer from 1 to 10; and
Z' is an integer from 1 to 4.
27. A composition according to claim 26 which contains about
1.0% to about 5.0% of the stabilizer composition, the percentages
being by weight based on the weight of the halogen-containing
organic polymer.
54

Description

12~4~ 7
1276-28-24
STABILIZERS FOR HALOGEN-CONTAINING
ORGANIC POLYMERS COMPRISING AN ORGANOTIN
MERCAPTIDE AND A DIESTER OF AN UNSATURATED DICARBOXYLIC ACID
-
BA XGROUND OF THE INVENTION
Field of the Invention
This invention relates to compositions which are capable of
stabilizing rigid (unplasticized) halogen-containing organic
polymers against the deteriorative effects of heat, light and
weathering. Such stabilizers comprise an organotin mercaptide
and/or an organotin sulfide, and a dialkyl ester of an ethy-
lenically unsaturated dicarboxylic acid. The invention also
relates to halogen-containing organic polymers stabilized with
such compositions.
Description of the Prior Art
It has long been known that halogen-containing organic
polymers, such as the commercially important poly (vinyl
chloride), are subject to deterioration or degradation when
exposed to heat and light. Various chemical compounds and
compositions have been developed to stabili'ze these polymers
against such deterioration. For the most part, these stabilizers
have been directed toward stabilization against heat, such as that
encountered during processing of the polymer and i~s fabrication
into articles. Among these heat stabilizers, some of the most
effective have been the organotin compounds. The organotin
compounds which have been found to be effective heat stabilizers
for halogen-containing organic polymers include a wide variety of
compounds. Mono- and dialkyltin carboxylates and mono- and
dialkyltin mercaptides, for example, have been employed
successfully as heat stabilizers.
Other organic, non-metallic compounds have also been found to
be useful as heat stabilizers for halogen-containing organic
polymers and are sometimes employed in combination with the
organotin stabilizers. For instance, U.S. Patent No. 3,379,679
discloses stabilizer compositions containing an organotin maleate
of the formula:

12~ ^'t;'
R
Il ~1 1 ~ 11 1~
R20-C-CH=CH-C-O-Sn-QC-CH=CH-C-OR2
Rl
and a maleate ester of the formula:
O O
~ 11 t~ ,
R30-C-CH=CH-C-OR3
where R, R1 and R2 are each alkyl or alkenyl of up to 12 carbon
atoms, or aryl, alkaryl or aralkyl of from 6 to 9 carbon atoms;
and R3 is hydrogen, alkyl or alkenyl of up to 12 carbon atoms, or
aryl alkaryl or aralkyl of from 6 to 9 carbon atoms, provided that
at least one of said R3 is other than hydrogen.
With the increased use of halogen-containing organic polymers
for rigid articles which will be exposed to light and weathering
for long periods of time (e.g. housing siding and window profiles)
it has become increasingly important to develop a stabilizer which
will not only protect the polymer against the high temperatures
encountered during processing and fabrication, but will also
protect the polymer against the long-term effects of light and
weathering. However, until the present invention, no single
stabilizer composition was completely satisfactory for protecting
the halogen-containing organic polymers against heat, light and
weathering. Thus, while an organotin compound, and in particular
the organotin mercaptides, provided good heat stability, they were
not acceptable weathering stabilizers. Likewise, the
aforementioned combination of organotin maleates and maleate
esters disclosed in U.S. Patent No. 3,379,679 does not provide
adequate heat stability, is incompatible with normally used
ingredients employed in commercial polymer formulations (commonly
called "microingredientsn), such as calcium stearate, and can
cause problems with eye irritation and offensive odors due to the
presence of the organotin maleate. Thus, the industry has been
unable to use organotin maleates as light stabilizers because of
the aforementioned problems. Instead, it chooses to use the
organotin mercaptides which overcome the problems of eye
irritation and incompatibility with microingredients, but which
give less than desired weathering and light stabilization.
~ 2

lZ543~'7
It has now been quite unexpectedly discovered that the
problems encountered with the prior art stabilizers can be
overcome while still providing excellent stabilization o~
halogen-containing organic polymers against heat, light and
weathering when stabilizers are employed which comprise organotin
sulfides, organotin mercaptides and/or organotin carboxylates in
combination with dialkyl esters of ethylenically unsaturated di-
carboxylic acids.

1~54~37~
SUMMARY OF THE INVENTION
In accordance with the present invention there are provided
compositions capable of stabilizing halogen-containing organic
polymers against the deteriorative effects of heat, light and
weathering, said composition comprising the product produced by
combining:
a. an organotin compound or mixture of organotin compounds
selected from the group consisting of organotin sulfides,
organotin mercaptides and mixtures thereof (hereinafter
referred to sometimes as "organotin-sulfur compounds");
b. in an amount sufficient to synergize the stabilization of
the halogen-containing organic polymer, but insufficient
to plasticize said polymer, an essentially non-lubricating
diester of a Cl-C10 alcohol and an ethylenically unsatura-
ted dicarboxylic acid having one carboxyl group on each
carbon atom of the ethenylene group (hereinafter referred
to sometimes simply as "diester"); and, optionally,
c. an organotin carboxylate or mixture of organotin
carboxylates.
Also in accordance with this invention there are provided
compositions capable of stabilizing halogen-containing organic
polymers against the deteriorative effects of heat, light and
weathering, said composition comprising the product produced by
combining:
a. an organotin compound or mixture of organotin compounds
selected from the group consisting of organotin sulfides,
organotin mercaptides, organotin carboxylates and mixtures
thereof; and
b. in an amount sufficient to synergize the stabilization of
the halogen-containing organic polymer, but insufficient to
plasticize said polymer, an essentially non-lubricating diester
of a C1-C10 alcohol and an ethylenically unsaturated dicarboxylic
acid, said diester having tbe formula:
~ R202 R202 R202 R
R200 ~ -Ç,-C C -~- -R201 ~ Z2oo-R2ol) -x ~ t' O-~,-C C-~,-O-R ~ z'
,

iz543t~>7
where:
R and R 3 each have from 1 to 10 carbon atoms and
are at each independent occurrence selected from alkyl,
alkenyl, cycloalkyl, cycloalkenyl, multivalent hydrocarbyl
group having a valence equal to z', multivalent hydroxyl
substituted hydrocarbyl group having a valence equal to z',
and--~R201 z2O ~ R204;
R201 is at each independent occurrence selected from alkylene,
alkenylene, cycloalkylene, cycloalkenylene, a multivalent
hydrocarbyl group and multivalent hydroxyl-substituted
hydrocarbyl group;
R202 is at each independent occurrence selected from hydrogen,
alkyl and alkylene ti.e. the alkylene group forms a ring with
the -C=C- group);
R204 is at each independent occurrence selected from hydrogen and
alkyl;
z200 is at each independent occurrence selected from -o-, -oC-, -C-,
-1~
-S-, -S-, and -S-;
t' is zero or an integer from 1 to about 20;
x' is zero or an integer from 1 to about 20 with the proviso that
if x'=0 or t~=0 then R200 i5_~R201 _ Z200) R204
y' is an integer from 1 to 10; and
z' is an integer from 1 to 4.
There is also provided in accordance with the present
invention a composition comprising a halogen-containing organic
polymer and, in an amount sufficient to stabilize said polymer
against the deteriorative effects of heat, light and weathering, a
stabilizer composition comprising the product produced by
combining:
a. an organotin compound or mixture of organotin compounds
selected from the group consisting of organotin sulfides,
organotin mercaptides and mixtures thereof;

i2S~37t7
b. in an amount sufficient to synergize the stabilization of
~he halogen-containing organic polymer, but insufficient
to plasticize said polymer, an essentially non-lubricating
diester of a Cl-C10 alcohol and an ethylenically unsatura-
ted dicarboxylic acid having one carboxyl group on each
carbon atom of the ethenylene group; and, optionally,
c. an organotin carboxylate or mixture of organotin
carboxylates.
There is further provided in accordance with the present
invention a composltion comprising a halogen-containing organic
polymer and, in an amount su~icient to stabilize said polymer
against the deteriorative effects of heat, light and weathering,
a stabilizer composition comprising the product produced by
combining:
a. an organotin compound or mixture of organotin compounds
~elected from the group consisting of organotin sulfides,
organotin mercaptides, organotin carboxylates and mixtures
thereof; and
b. in an amount sufficient t~ synergize the stabilization of
the halogen-containing organic pol~mer, but insufficient to
plasticize said polymer, an essentially non-lubricating diester
of a C1-C10 alcohol and an ethylenically unsaturated dicarboxylic
acid, said diester having the formula:
I R202 R202 R202 R
R200 ~ ~-C-C~- G -~ O R201 ~ z200 R201 ) ) O-&-C C-&-O-R 3)z~
where:
R200 and R203 each have from 1 to 10 carbon atoms and
are at each independent occurrence selected from alkyl,
alkenyl, cycloalkyl, cycloalkenyl, multivalent hydrocarbyl
group having a valence equal to z', multivalent hydroxyl
substituted hydrocarbyl group having a valence equal to z',
and -t R201 z200) 204
R201 is at each independent occurrence selected from alkylene,
alkenylene, cycloalkylene, cycloalkenylene, a mul`tivalent
hydrocarbyl group and multivalent hydroxyl-substituted
hydrocarbyl group;

12S~3~7
R202 is at each independent occurrence selected from hydrogen,
alkyl and alkylene (i.e. the alkylene group forms a ring with
the -C=C- group);
R204 is at each independent occurrence selected from hydrogen and
alkyl;
O .0
Z is at each independent occurrence selected from --, -OC-, -C-,
.0 -O
-S-, -S-, and -S-;
.0
t' is zero or an integer from 1 to about 20;
x' is zero or an integer from 1 to about 20 with the proviso that
if x'=0 or t'=0 then R200 is ~R201 _ z200 ~ R2o4;
y' is an integer from 1 to 10; and
z' is an integer from 1 to 4.
;, ~

12S~3~ 7
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
,
The halogen-containing organic polymers which are stabilized
by the stabilizer compositions of this invention and which are
useful in the polymer compositions of this invention include, for
example, halogenated polyolefin homopolymers, halogenated
polyolefin copolymers, polymer blends containing a halogenated
polyolefin homopolymer or copolymer, vinyl halide homopolymers,
vinyl halide copolymers and polymer blends containing vinyl halide
homopolymer or copolymers. The vinyl halide homopolymers, vinyl
halide copolymers and polymer blends containing vinyl halide
homopolymers or vinyl halide copolymers usable in the practice of
this invention may be, for example, (1) polyvinyl chloride,
polyvinylidene chloride, polyvinyl bromide, polyvinyl fluoride,
polyvinylidene fluoride, (2) copolymers of vinyl chloride with a
copolymerizable ethylenically unsaturated monomer such as
vinylidene chloride, vinyl acetate, vinyl butyrate, vinyl
benzoate, diethyl fumarate, diethyl maleate, other alkyl fumarates
and maleates, vinyl propionate, methyl acrylate, 2-ethylhexyl
acrylate, butyl acrylate, ethyl acrylate, and other alkyl
acrylates, methyl methacrylate, ethyl methacrylate, butyl
methacrylate, hydroxyethyl methacrylate and other alkyl
methacrylates, methyl alpha-chloroacrylate, styrene, vinyl ethers
such as vinyl ethyl ether, vinyl chloroethyl ether, vinyl phenyl
ether; vinyl ketones such as vinyl methyl ketone, vinyl phenyl
ketone, 1 -fluoro-l-chloroethylene, acrylonitrile,
chloroacrylonitrile, allylidene diacetate, chloroallylidene
diacetate, ethylene and propylene, and (3) polymer blends such as
blends of polyvinyl chloride and polyethylene, polyvinyl chloride
and chlorinated polyethylene, polyvinyl chloride and polymethyl
methacrylate, polyvinyl chloride and polybutylmethacrylate,
polyvinyl chloride and polystyrene, polyvinyl chloride and
acrylonitrile-butadiene-styrene copolymer, and polyvinyl chloride
and polyethylene and polymethyl methacrylate. Typical vinyl
halide copolymers usable in this invention include vinyl
chloride-vinyl acetate (87:13), vinyl chloride-vinylidene chloride
(95:5), vinyl chloride-diethyLfumarate (95:5), vinyl
chloride-trichloroethylene (95:5) and vinyl chloride-2-ethylhexyl
acrylate (80:20). The polymer blends usable in the practice of
this invention comprise physical blends of at least two distinct
polymeric species and contain from 25 to 95 weight percent of
vinyl halide homopolymer. The vinyl halide copolymers usable in
the practice of this invention are copolymers comprising from 25
to 95 mole percent vinyl halide units. Of these polymers, the
vinyl halide homopolymers are preferred.

i~4~;~
The organotin-sulfur compounds useful in the practice of this
invention are organotin sulfides, organotin mercaptides and
mixtures thereof. The organotin sulfides are compounds which have
one or more tetravalent tin atoms which each have at least one
direct tin to carbon bond with the remainder of the valences on
the tin atom being taken up by sulfur atoms. These organotin
sulfides may be further described by the following general
formulas:
(I) (R-Sn)2S (also written as (R-Sn-Sl 5)4)
(II) R2Sn=S (also written as (R2SnS)3)
where R is as defined below.
Examples of organotin sulfides useful in the practice of this
invention include, but are not limited to, the following:
(C H -Sn) S
(C8H17 Sn)2
(C4Hg)2Sn=S
(C8H17)2Sn=S
The organotin mercaptides useful in this lnvention are
compounds which have at least one tetravalent tin atom which has
one or two direct tin to carbon bond and at least one tin to
sulfur to carbon (Sn-S-C) bond. These organotin mercaptides may
be further described by the following general formulas:
(III) R-Sn-X
~,
(IV) Rn-Sn-Xp and

~ l~S~3~7
c , a ~ c
Sn- Y~Sn- Y ~ Sn wherein
Xd Xb Xd
X is at each independent occurrence selected from
O O O
2 11 8 il 4 1l
-SR , -O-C-R , -OC-R -C-O-R8 or
O O
O-C-R -C-o-R3-o-R8 with the proviso that; (1) at least
one X in formulas III and IV is -SR2 and (2) in formula
V at least one X is -SR or at least one Y is -S-R3~
o
4 "
-S-R -C-O-,
O O
-S-R4-c-o-R3-o-c-R4-s-~ or
~ O O
-S-R3-o-C-R4-S or -S-R3-oC-R6-C-o-R -S-;
Y is at each independent occurrence selected from
O O O
-(S)-Vr -S-R3-W-, -S-R4-C-o-, -S-R4-C-o-R3-o-c-R -S-,
O O O O O
-S-R3-o-C-R4-S-, -S-R3-0-C-R6-C-o-R3-s-, -O-C-R6-C-O-,
O O O
-o-c-R6-c-o-R3-o-c-R6-c-o-;
is at each independent occurrence selected from oxygen or
sulfur;
R is at each independent occurrence selected from alkyl, alkenyl,
cycloalkyl, cycloalkenyl,
O O O O
-R9-C-R8, -R9-C-O-R12, -R9-O-C-R , -CH-C-R
O=C
R14
-R9_o-Rl2~ -R -CN;

1254377
R is at each independent occurrence selected from alkyl, alkenyl,
O o O O
cycloalkyl, cycloalkenyl, -R4-C-o-R , -R3-o-C-R8, -R3-o-c-R4-c-o-R7
O O
-R4-C-o-R3-o-C-R8, -R3-S-R7,or -R -O R ;
R3 is at each independent occurrence selected from alkylene of at
least 2 carbon atoms, alkenylene of at least 2 carbon atoms,
cycloalkylene, or cycloalkenylene;
R is at each independent occurrence selected from alkylene,
alkenylene, cycloalkylene, or cycloalkenylene;
R6 is at each independent occurrence selected from a carbon-carbon
bond, or R4;
R7 is at each independent occurrence selected from -~ or R8;
R8 is at each independent occurrence selected from alkyl,
alkenyl, cycloalkyl, or cycloalkenyl;
R is at each independent occurrence selected from C1 to C4
alkylene;
R12 is at each independent occurrence selected from -H or a
monovalent Cl to C20 hydrocarbon radical;
R13 and R14 are at each independent occurrence selected from Cl to
C20 alkyl or 1 t 20 Y;
at each independent occurrence n=1 or 2 and p=4-n;
at each independent occurrence a = 1 or 2; b = 2-a;
c = 1 or 2; d = 3-c; and q = 0 or an integer from 1 to 4
inclusive; and
v is at each independent occurrence selected from an integer
from 1 to 8 inclusive.
In the above formulas, it is understood that formula V
includes those organotin mercaptides which are cyclic, i.e. where
formulas V would be written:
., ,

lZS~3~7
^
Sn Y or
~ ~ Y
Sn Sn
y~
Examples of organotin mercaptides useful in the practice of
this invention include, but are not limited to:
(1) alkyltin alkylthioalkanoates, including monoalkyltin
tris(alkylthioalkanoates) and dialkyltin bis(alkylthioalkanoates),
such as
Il
cH3sn(scH2coc8Hl7)3
monomethyltin tris(isooctylthioglycolate)
O
tC8H17)2Sn(scH2cOc8Hl7)2
dioctyltin bis(isooctylthioglycolate)
, C4 9 ( 2 8 17)3
monobutyltin tris(isooctylthioglycolate)
(C4H9)2Sn(scH2cOc8Hl7)2
dibutyltin bis(isooctylthioglycolate)
(2) alkyltin mercaptoalkylalkanoates, including the monoalkyltin
tris(mercaptoalkylalkanoates) and dialkyltin
bis(mercaptoalkylalkanoates), such as

l~S'~7'~'
CH3Sn(SCH2CH20C(CH2)8CH-CH(CH2)7 3)3
monomethyltin tris(mercaptoethyloleate)
(cH3)2sn(scH2cH2oc(cH2)gcH=cH(cH2)7cH3)2
dimethyltin bis(mercaptoethyloleate)
O O
C4Hg-O-CCH2CH2-Sn(SCH2CH20C(CH2)7CH3)3
mono(beta-carbobutoxyethyl)tin tris(mercaptoethylpelargonate)
( 4 9)2Sn(SCH2CH20C(CH2)7CH3)2
dibutyltin bis(mercaptoethylpelargonate)
(3)bis(alkyltin alkylthioalkanoate) sulfides, including the
bis(monoalkyltin di(alkylthioalkanoate))sulfides and
bis(dialkyltin mono(alkylthioalkanoate))sulfides, such as
O O
(C8H170CCH2S)2-Sn-S-S~n(SCH2COC8H17)2
3 3
bis(monomethyltin di(isooctylthioglycolate)) sulfide
O o
C H OCCH S - Sn -S- Sn - SCH2COC8H17
(CH3)2 (CH3)2
bis(dimethyltin mono(isooctylthioglycolate))sulfide
O O
(C8H170CCH2S)2 - ISn - S - Sln - (SCH2COC8H17)2
C4Hg C4Hg
bis(monobutyltin di(isooctylthioglycolate))sulfide
~. o
C8H170CCH2S - Sn - S - Sn - SCH2COC8H17
(C4Hg)2 (C4Hg)2
bis(dibutyltin mono(isooctylthioglycolate))sulfide

1;254377
(4) bis(alkyltin mercaptoalkylalkanoate)sulfides, including
bis(monoalkyltin di(mercaptoalkylalkanoate))sulfides and
bis(dialkyltin mono(mercaptoalkylalkanoate))sulfides, such as
'O . O
(CH3(CH2)7CH=CH(CH2)8COCH2CH2S)2Sn-S-SIn-(SCH2CH20C(CH2)8CH=CH(CH2)7CH3)2
CH3 CH3
bis(monomethyltin di(mercaptoethyloleate))sulfide
O O
CH3(CH2)7CH=CH(CH2)8COCH2CH2S - Sln-S - S\n-SCH2CH20C(CH2)8CH=CH(CH2)7CH3
(CH3)2 (CH3)2
bis(dimethyltin mono(mercaptoethylole.ate))sulfide
O O
(CH3(CH2;7COCH2CH2S)2Sln - S - Sln -(SCH2CH20C(CH2)7CH3)2
CH3 CH3
bis(monomethyltin di(mercaptoethylpelargonate))sulfide
O O
ll 11
CH3(CH2)7COCH2CH2S-Sln - S - Sln - SCH2CH20C(CH2~7CH3
(C8H17)2 (C8Hl7 2
bis(dioctyltin mono(mercaptoethylpelargonate))sulfide
(5) alkyltin alkylmercaptides, including monalkyltin
tris(alkylmercaptides) and dialkyltin bis(alkylmercaptides) such
as
CH3-Sn(scl2H23 3
monomethyltin tris(lauryl mercaptide)
(CH3)2-Sn(SC12H23)2
dimethyltin bis(lauryl mercaptide)
C4Hg-Sn(scl2H23 3
monobutyltin tris(lauryl mercaptide)
(C4Hg)2-Sn(SC12H23)2
dibutyltin bis(lauryl mercaptide)
Particularly useful in the practice of this invention are
mixtures of monoalkyltin and dialkyltin mercaptides.

12S~3'7'7
The organotin carboxylates which may be employed in accordance
with this invention are compounds which have tetravalent tin atoms
which each have one or two direct tin to carbon bonds, the
remainder of the bonds on the tin atoms being tin to oxygen to
carbonyl, i.e. tin-carboxyl (Sn-O-C-) bonds. These organotin
carboxylates may be further described by the following general
formulas:
(VI) Rn-Sn-Zp
- RlC Rla R~c
(VII) qn - A-~Sn - A ~ /n
2d Zb Zd
(VIII) R2
Sn-A
A - Sn
R2
wherein R, n, p, a, b, c, d and q are as previously defined;
t~ O O O O
Z is -o-C-R7, -o-C-R4-C-o-R7 or -o-C-R4-C-o-R3-o-R ;
.0 0 0 0 0 0
Ii 4 ll ll 4 ll 3 ll 4 1l
A is -O-C-R -C-O- or -O-C-R -C-O-R -OC-R -C-o-;
R3, R4, R7 and R8 are as previously defined; and
r=0 or an integer, preferably about 1-20.
Examples of organotin carboxylates which are useful in the
practice of this invention include, but are not limited to,
alkyltin alkyl maleates, such as dibutyltin bis(butyl maleate),
and polymeric alkyltin maleates, such as dibutyltin maleate.

iZ54~'77
The compounds employed in combination with the above-described
organotin-sulfur compounds and/or organotin carboxylates in the
practice of this invention are diesters o~ ethylenically unsatura-
ted dicarboxylic acids having one carboxyl group on each carbon
atom of the ethenylene group. These diesters are represented by
compounds having the formulas:
102 R102
(IX) R1 ~ R101 0 _ ~ C C C----Rl
where R100 and R103 are the same or different, and are at each
independent occurrence alkyl, alkenyl, cycloalkyl, cycloalkenyl,
or a multivalent hydrocarbyl or hydroxyl-substituted hydrocarbyl
group such as alkylene, alkenylene, cycloalkylene,
cycloalkenylene, alkynylene or tetravalent carbon;
R10l is at each independent occurrence a carbon-oxygen bond,
alkylene or alkenylene, with the proviso that the total number of
carbon atoms in R100 plus R10l is from 1 to 10 and the total
number of carbon atoms in R 03 plus R101 is from 1 to 10;
R102 is at each independent occurrence selected from hydrogen,
alkyl and alkylene (i.e. the alkylene group forms a ring with the
-C=C- group); and
t is an integer, preferably from 1 to about 20.
(IXa)
~ R202 R202 R o R .
R200 _ ~O-~-C C -,C,-O-R 1 ~ Z2oo-R2ol ) ,) , o-C-C C-C-o-R203 z'
where:
R200 and R203 each have from 1 to 10 carbon atoms and
are at each independent occurrence selected from alkyl,
alkenyl, cycloalkyl, cycloalkenyl, multivalent hydrocarbyl
group having a valence equal to z', multivalent hydroxyl
substituted hydrocarbyl group having a valence equal to z',
and -~ R201 z200) 204
R201 is at each independent occurrence selected from alkylene,
alkenylene, cycloalkylene, cycloalkenylene, a multivalent
hydrocarbyl group and multivalent hydroxyl-substituted
hydrocarbyl group;
16

~2S4~3'7'~
R202 is at each independent occurrence selected from hydrogen,
alkyl and alkylene (i.e. the alkylene group forms a ring with
the -C=C- group);
R204 is at each independent occurrence selected from hydrogen and
alkyl;
O O
z200 is at each independent occurrence selected from -o-, -Oc-,
O O
Il 11
-S-, -S-, and -S-;
t' is zero or an integer from 1 to about 20;
x' is zero or an integer from 1 to about 20 with the proviso that
if x'=0 or t'=0 then R200 is_~R201 z200 ~ R204;
y I i8 an integer from 1 to 10; and
z' is an integer from 1 to 4.
It should be noted that the diesters useful in this invention
include both the cis and trans isomers.
The diesters usefùl in accordance with this invention do not
function as lubricants in halogen-containing polymer compositions
based on rheologi*cal testing commonly used in the industry, such as
with a ~rabender rheometer. The diesters are essentially non-lubricating
in that they do not enhance the stability of the halogen-containing
polymer by physically modifying the polymer melt. It is believed that
this is due to the relatively short chain (Cl to C10) alcohol
used to prepare the diesters.
Examples of the diesters according to formula IX which are
useful in this invention include, but are not limited to, the
following compounds which are identified by both chemical name (or
structure~ and by the substitutents in formula IX:
R10O Rlol R102 R103 t
dioctyl maleate C8H17 -H C8 17
dibutyl maleate 4 9 -H 4 9
di(2-ethylhexyl)C4HgCHCH2~ - -H C4Hg-CHCH2-
maleate C2H5 C2H5
';~ *Trademark

lZS~3'77
R100 R101R102 R103
dibutyl C4Hg -(CH2)4- C4H9
tetrahydrophthalate
methyl cyclohexyl CH3- - -
maleate
diallyl maleateCH2=CH-CH2- - -H -CH2-CH=CH2
octyl methyl C8 17 -H. -CH3
maleate
butyl octyl 4 9 -H -C8H17
maleate
diisoctyl 8 17 -H -C8H17
maleate
butyl (2-e.thylhexyl) C4Hg- - -H -CH2CH-C4H9
maleate C2H5
dimethyl maleate 3 -H -CH3
bis(butylmaleate) -CH- -CH2- -H 4 9 2
glycerate OH
bis(butylmaleate) -CH2CH2- - -H 4 9 2
ethyleneglycolate
bis(butylmaleate) (CH2)4 -H C4H9 2
butyleneglycolate
bis(methylmaleate) -(CH2)4- - -H -CH3 2
butyleneglycolate
bis(allylmaleate) ( 2)4 -H -CH2CH=CH2 2
butyleneglycolate
18

i;~S~;~'7'7
Rl00 Rl0Rl0 Rl 3 t
O O
C-(CH2OCCH=CHCOCH3)4 -C- -CH2- -H ~ -CH3 4
o
C2H5-C(CH2OCCH= 2 5 ~ -CH2- -H -C4H9 3
CHICOC4H9)3
o
I
2 OCH2/C -CH2- -H -C8Hl7 2
I . O O HOCH
l ll 11 2
C(CH2OCCH=CHCCgH17)2
CH2H
OH 1 1
CH(CH2OCCH=CHCOC2H5)2 HO-CH- -CH2- -H 2 5 2
O O O
Il 11 11
CH3OCCH=CHCOCH2OCCH -CH2- - -H -CH3 2
CH
1
CH3
Further examples include the fumarate counterparts to the
above maleate diesters. Mixtures of maleate and fumarate diesters
(which are commonly formed during the preparation of these
diesters) may also be employed.
Examples of the diesters according to formula IXa which are
useful in this invention include, but are not limited to, the
following compounds which are identified by both chemical name
(and/or structure) and by the substituents in formula IXa:
diethyleneglycol bis(butyl maleate)
11 O
C4H9~o-c-cH=cH-co-cH2cH2-o-cH2-cH2-oc-cH=cH-c-oc4H9
R200 R202z200 R201 R203 _ t' z'
C4Hg -H-O -CH2CH2- -C4H9
~f`~
.~
19

lZS4;~ 7
triethylene glycol bis(butyl maleate)
O O o' p
C H O-C-CH=CH-CO-CH CH -O-CH -CH2-O-cH2cH2-o~-cH=cH-c-oc4H9
R200 R 02 z200 R R 03 x' t' z'
4 9 -H _o_ -CH2CH2- c4 9
tetraethyleneglycol bis(butyl maleate)
0 1l I' 1l
C4H9o-c-cH=cH-c-o-cH2cH2 -(OCH2CH2)3- o-C-CH=CH-C-C4H9
R200 R_ z200 R201 R x' t' z
c4 9 -H -O- -CH2CH2- -C4H9 3
ethyleneglycol glycolate bis(butyl maleate)
C4H90-C-CH=CH-C O-CH2C CH2CH~oCCH2-o-C-CH=CH-C-O-C4Hg
R200 R202 z200 R201 R 3 x' t' z
.0 0
-C4H9 -H -COCH2CH2OC- -CH2 C4 9
Poly(diethyleneglycol maleate) bis(methyl maleate)
CH3~ 0-c-cH=cH-c-ocH2cH2ocH2cH2~t~o-c-cH=cH-c-oc~3
R_ R202 z200 R201 R203 . x' t' z
-CH3 -H -O- -CH2CH2- -CH3 1 2-20
r ~.1 i

i25~ 7
diethyleneglycol bis(methoxy ethyl maleate)
O O O O
CH30CH2CH20--C--CH=CH--C--O--CH2CH2-O--CH2CH2-0-C-CH=CH--C--oCH2CH2oCH3
R200 202 200 R201 R2o3 x' t' z'
CH3OCH2CH2- -H ~O~ -CH2cH2- -CH2cH2ocH3
OH O O O O
11 11 Ir 11
HC ~cH2o-c-cH=cH-c-ocH2cH2ocH2cH2o-c-cH=cH-c-ocH3)2
R R202 Z R201 R203 x' t' z'_
OH
HC-CH2- -H -O--CH2CH2- -CH3 1 1 2
CH2 -
O O
11 11
CH3CH20CH2CH20-C-CH=CH-C-O'CH2CH20CH2CH3
R200 and R203 R202 R201 z200 R204 x' t' z'
-- _ _ _ _ _
201 z2 ~ R204 -H -CH2CH2 o C 2 3 1 0
thiodiglycol bis(butyl maleate)
O O O
1~ 1~ 11 11
C4H9O-C-CH=CH-C-O-cH2cH2-s-cH2cH2-o-c-cH=cH2-c-oc4H9
R200 R202 z200 R201 R2o3 x' t' z'_ _
c4 9 -H- -S- -CH2CH2- 4 9
-
21

`~;~S43 ~ 7
bis(ethyl sulfoxide)-2,2'-bis(butyl maleate)
O O O O
R 11 11 11 11
C4HgO-C--CH=CH-C-o-CH2CH2--S--CH2CH2-0-C-CH=CH-C-OC4Hg
R R202 z200 R201 R2o3 x' t' z'
O'~
4 9 -H- -S- -CH2cH2- 4 9
bis(ethyl sulfone)-2,2'-bis(butyl maleate)
o o o O O
n
o
R_ R202 z200 R201 R2o3 x' t' z
4 9 -H- -S- -CH2CH2- C4H9
o
Further examples include the fumarate counterparts to the
above maleate diesters. Mixtures of maleate and fumarate
diesters (which are commonly formed during the preparation of
these diesters) may also be employed.
The diesters which are preferred in the practice of this
invention are those according to formula IXa where R200 is C1 to
C10 alkyl, R201 is C1 to C4 alkylene, R202 is hydrogen, z200 is
-0-, t' is at least 1 but not more than 20 and x' is at least 1
but not more than 3.
As used in the above formulas and throughout this specifi-
cation, the term alkyl represents monovalent, straight or branched
chain, saturated hydrocarbon radicals containing, for example, 1
to 20 carbon atoms, the term alkylene refers to divalent, straight
or branched chain saturated hydrocarbon radicals containing, for
example, 1 to 20 carbon atoms and the term alkynylene refers to
trivalent straight or branched chain saturated hydrocarbon radi-
cals containing, for example, 1 to 20 carbon atoms. The term
alkenyl refers to monovalent, straight or branched chain C2 to C20
hydrocarbon radicals containing at least one double bond, and the
22

, lZS~3'~7
term alkenylene refers to divalent C2 to C20 hydrocarbon radicals
containing at least one double bond. The term cycloalkyl
represents monovalent C3-C8 saturated cycloaliphatic radicals;
cycloalkylene refers to divalent C3-C8 cycloaliphatic radicals;
cycloalkenyl refPrs to
monovalent C5-C8 cycloaliphatic radicals containing at least one
double bond; and cycloalkenylene represents divalent C5-C8 cyclo-
aliphatic radicals containing at least one double bond. The term
multivalent hydrocarbyl group refers to groups such as alkylene,
alkenylene, cycloalkylene, cycloalkenylene, alkynylene and
tetravalent carbon, and the term multivalent hydroxyl-substituted
hydrocarbyl group refers to groups such as hydroxyl-substituted
alkylene, alkenylene, cycloalkylene, cycloalkenylene alkynylene
and tetravalent carbon.
The amount of organotin-sulfur compound and/or organotin
carboxylate and diester in the stabilizer compositions of this
invention will depend upon several factors, including, but not
limited to, the particular organotin-sulfur cGmpound, diester and
organotin carboxylate employed, the particular resin which is
intended to be stabilized, the severity of the heat, light and
weathering to which the resin will be subjected and the degree of
stabilization desired. Thus, the amount of organotin-sulfur
compound and/or organotin carboxylate and diester may vary con-
siderably, it being required only that the stabilizer composition
contain enough of each component to stabilize a halogen-containing
organic polymer against the deteriorative effects of heat, light
and weathering, and that the diester be present in an amount which
will synergize such stabilization while at the same time being
insufficient to plasticize the polymer.
In general, the stabilizer compositions in accordance with
this invention which contain an organotin-sulfur compound and
diester according to formula IX employ these compounds in a
molar ratio of organotin-sulfur compound to diester (organotin-
sulfur compound/formula IX diester) of from about 2/1 to about 1/8,
preferably from about 1/2 to about 1/6. This corresponds to a
stabilizer composition which contains roughly from about 20% to
about 75% formula IX diester, with the balance being organotin-
sulfur compound, the percentages being by weight based on the com-
bined weight of the diester and organotin-sulfur compound. These
weight percentages may, of course, vary considerably depending
upon the particular compounds selected and their molecular weights.
~';
,. ..

~ S~;377
When the stabilizer compositions in accordance with this
invention employ an organotin-sulfur compound, an organotin car-
boxylate and a formula IX diester, the amount of diester used is
normally the same as that employed when the organotin-sulfur
compound and diester are used alone. Thus, the molar ratio of
organotin compounds (i.e. organotin-sulfur compound plus organotin
carboxylate) to diester would remain about 2/1 to about lt8,
preferably about 1/2 to about 1/6. However, the molar ratio of
organotin-sulfur compound to organotin carboxylate (organotin-
sulfur compound/organotin carboxylate) will generally be from
about 1/1 to about 1/5. In terms of weight percent, the
stabilizer would contain roughly about 15% to about 60% formula
IX diester with the balance being organotin-sulfur compound and
organotin carboxylate, the percentages being by weight based on
the combined weight of diester, organotin-sulfur compound and
organotin carboxylate. The organotin portion of the stabilizer,
would contain about 10% to about 50% organotin-sulfur compound and
about 50% to about 90% organotin carboxylate, in this case the
percentages being by weight based on the combined weight of only
the organotin-sulfur compound and organotin carboxylate.
The stabilizer compositions in accordance with this invention
which contain an organotin sulfide, organotin mercaptide,
organotin carboxylate or mixture thereof and a diester according
to formula IXa employ these compounds in a molar ratio of
organotin compound to formula IXa diester ~organotin
compound/diester) of from about 2/1 to about 1/8, preferably
from about 1/2 to about 1/6. This corresponds to a stabilizer
composition which contains roughly from about 20% to about 75%
formula IXa diester, with the balance being organotin compounds,
the percentages being by weight based on thecombined weight of
the diester and organotin compound. These weight percentages
may, of course, vary considerably depending upon the particular
compounds selected and their melecular weights. When the
organotin portion of the stabilizer contains a mixture of an
organotin-sulfur compound and an organotin carboxylate the molar
ratio of organotin-sulfur compound to organotin carboxylate
(organotin-sulfur compound/organotin carboxylate) will generally
be from about 1/1 to about 1/5. In terms of weight percent, the
stabilizer would contain roughly about 25% to about 60~ diester
with the balance being organotin-sulfur compound and organotin
carboxylate, the percenta~es being by weight based on the
combined weight of only the organotin-sulfur compound and
organotin carboxylate.
~r 24

12S~3~7t~
As with the relative amounts of organotin-sulfur compounds,
diester and organotin carboxylate, the amount of stabilizer
composition employed in the halogen-containing organic polymer
compositions of this invention can vary considerably. The minimum
amount of stabilizer in the polymer composition is that amount
which will stabilize the polymer against the deteriorative effects
of heat, light and weathering. While this minimum amount can vary
depending upon the same factors referred to above with respect to
the stabilizer compositions, in general about 1.0% to about 5.0%
of stabilizer composition based on the weight of halogen-
containing organic polymer will be sufficient to impart
the desired properties to the polymer composition in most cases.
Amounts greater than this minimum level of stabilizer can, of
course, be employed, although at some point the increase in
stabilization of the polymer is not commensurate with the
additional amount of stabilizer employed. Thus, while there is no
critical upper limit to the amount of stabilizer which may be
employed, amounts in excess of about 8% do not give an increase in
effectiveness which will justify the use of these higher amounts
of stabilizer. In fact, amounts above about 8-10% of stabilizer
composition may begin to plasticize the polymer and change its
physical properties dramatically.
The stabilizer compositions of this invention can be made
quite simply. For example, the organotin-sulfur compounds,
diester and, if used, organotin carboxylate can be simply combined
physically as by mixing, blending, stirring, shaking or the like.
Likewise, the halogen-containing organic polymer compositions of
this invention may be prepared by physically blending the stabi-
lizer composition and the polymer (plus any desired additives) in
any convenient manner until the stabilizer composition is
thoroughly dispersed throughout the polymer composition. In
normal commercial practice this is accomplished by high intensity
mixing.
The stabilized polymer compositions of this invention are
useful to form a variety of rigid articles of manufacture, e.g.
housing siding, window profiles and the like, and are especially
useful in those articles which are exposed to light and weather-
ing. A variety of conventional techniques may be employed to
shape the polymer composition into the desired article.
The following examples illustrate the present invention.
Unless otherwise indicated, all parts and percentages in the
examples and throughout this specification are by weight.

1~5'13','7
Examples 1-6 and I-VII demonstrate the superior heat, light
and weathering stabilization of compositions according to this
invention which contain an organotin-sulfur compound and a
diester of the formula IX type, or an organotin-sulfur compound,
formula IX type diester and an organotin carboxylate.
EXAMPLES 1-6
The stabilizer compositions indicated in Table I were each in
turn blended with a standard poly (vinyl chloride) formulation
containing:
INGREDIENT PARTS BY WEIGHT
Poly (vinyl chloride)-Geon 103 EP 100.0
sold by B.F. Goodrich (K=68)
Process aid 1.5
Impact modifier 6.0
Pigment Approx. 1.0
Paraffin wax 1.2
Partially oxidized polyethylene 0.25
Each resulting polymer composition was then formed into a
plaque and tested for stability to light and weathering by ex-
posing it to ultraviolet light (W) and moisture in a Q-Panel Q W
accelerated weathering tester. Each plaque was weathered at 50C
by exposing it to 4 hours of W followed by 4 hours of a moisture
condensation cycle. This was repeated until the plaque had been
exposed for 750 hours, samples being taken for evaluation every
150 hours. The results of these tests are summarized in Table I.
*Trademark

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12S~37~7
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12S43~77
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~ZS4~77
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iZ543~7
The above results demonstrate that:
1. Organotin-sulfur compounds are poor weathering
stabilizers. For instance Control 1, Control 2 and Control 3
discolor severely after only about 150 hours.
2. Organotin carboxylates are adequate weathering
stabilizers as demonstrated in Control 4.
3. The weathering stabilization of organotin carboxylates is
improved only slightly, if at all, by their use in combination
with diesters. (Control 4a shows very little improvement over
Control 4.)
4. Stabilizers containing organotin-sulfur compounds and
diesters provide excellent weathering stability. This excellent
stabilization, as shown in Ex. No. la-lf, Ex. No. 2 and Ex. No. 3,
is quite unexpected in view of the poor weathering efficiency
of the organotin-sulfur compounds alone and the failure of the
diesters to significantly improve the efficiency of the organotin
carboxylates.
5. Stabilizers containing organotin-sulfur compounds,
diesters and organotin carboxylates also exhibit excellent
weathering stabilization (see Control 5 vs. Ex. No. 5a-5i and
Control 6 vs. Ex. No. 6). The excellent stabilization provided by
these compositions is surprising in that they contain an
ingredient known to exhibit poor weathering stabilization, i.e.
the organotin-sulfur compound. Thus, one would expect this three
component system to perform worse than the organotin
carboxylate/diester stabilizer. However, precisely the opposite
occurs. When some of the organotin carboxylate of Controls 5 and
6 is replaced with organotin-sulfur compouncl, the weathering
efficiency, rather than decreasing as expected, improves
dramatically.
EXAMPLES I-VII
The stabilizer compositions indicated in Table II were each
in turn blended with the same standard poly (vinyl chloride)
formulation used for the weathering stability tests.
Each resulting polymer composition was then tested for
stability to heat by milling on a two roll dynamic mill at about
180C. Samples of each composition were taken after every 2
minutes of milling and examined for degradation and discoloration.
The results are indicated in Table II.

l~S~37';'
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i~S~37~7
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lZS~;37~7
The heat stability results shown in Table II demonstrate that:
1. Organotin-sulfur compounds are excellent heat stabilizers
(see Controls I, II and III).
2. Employing diesters with organotin-sulfur compounds does
not adversely effect nor imporve the organotin-sulfur compounds'
heat stabilizing efficiency. (See Examples I, II, III and III').
3. Organotin carboxylates are extremely inefficient heat
stabilizers as demonstrated in Control IV. Also, when the
organotin carboxylates are employed in PVC formulations contain-
ing calcium stearate (a common ingredient in such formulations)
their efficiency decreases even further (see Control IV').
4. The use of diesters with the organotin carboxylates does
not significantly improve the organotin carboxylates' heat
stabilization in PVC formulations which do not contain calcium
stearate (see Control V) or for those formulations which do
contain calcium stearate (see Control V').
5. Unexpectedly, the addition of the organotin carboxylate
to a stabilizer containing an organotin-sulfur compound and a
diester still produces a stabilizer composition which yields
acceptable heat stability. This is surprising in view of the
extremely poor efficiency of the organotin carboxylate and the
fact that a portion of the efficient organotin-sulfur compound is
replaced by the inefficient organotin carboxylate (see Example I
vs. Examples V and V').
To summarize the results of Tables I and II, no synergism in
either weathering or heat stabilization is observed for composi-
tions containing organotin carboxylates and diesters. Synergism
in weathering stability is, however, evident in those stabilizers
containing organotin-sulfur compounds and diesters. Likewise,
synergism has been found in both weathering and heat stability
for compositions containing organotin-sulfur compounds, diesters
and organotin carboxylates. These cases of synergism are
unexpected since at least one of the compounds used in the
synergized compositions are very inefficient stabilizers, yet
their addition to the stabilizer system produces markedly
superior results.
36

12S~;~7'7
Examples 7-8 and VIII-IX demonstrate the superior heat, light
and weathering stabilization of compositions according to this
invention which contain an organotin sulfide, organotin
mercaptide, organotin carboxylate or mixtures thereof in
combination with a diester of .he formula IXa type.
The stabilizer compositions indicated in Table A were each in
turn blended with a standard poly(vinyl chloride) formulation
containing:
INGREDIENTPARTS BY WEIGHT
Poly(vinyl chloride)-Geon 103EP100.0
sold by B.F. Goodrich (K=68)
Process aid 1.5
Impact modifier 6.0
Pigment approx. 1.0
Paraffin wax 1.2
Partially oxidized polyethylene0.25
Each resulting polymer composition was then formed into a
plaque and tested for stability to light and weathering by
exposing it to ultraviolet light (W) and moisture in a Q Panel
QUV accelerated weathering tester. Each plaque was weathered at
50C by exposing it to 4 hours of W followed by 4 hours of a
moisture condensation cycle. This was repeated until the plaque
had been exposed for 750 hours, samples being taken for
evaluation every 150 hours. The results of these tests are
summarized in Table A.
*Trademark
~.

12S4377
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12S4377
The above results demonstrate that:
1. Organotin-sulfur compounds are poor we~thering stabili-
zers. For instance, Control No. 7 and Control No. 8 show severe
discoloration at the 150 hour point.
2. Stabilizers containing organotin-sulfur compounds and
diesters of the formula IXa type provide excellent weathering
stability, as shown in Ex. No. 7a-7f and Ex. No. 8.
Stabilizer compositions in accordance with this invention
which contain an organotin carboxylate and diester of the formula
IXa type also exhibit excellent weathering performance.
EXAMPLES VI I I - IX
The stabilizer compositions indicated in Table B were each in
turn blended with the same standard poly(vinyl chloride)
formulation used for the weathering stability tests. Each result-
ing polymer composition was then tested for stability to heat by
milling on a two roll mill at about 180C. Samples of each
polymer composition were taken after every 2 minutes of milling
and examined for degradation and discoloration. The results are
indicated in Table B.

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lZS~377
The heat stability results shown in Table B demonstrate that:
1. Organotin-sulfur compounds are excellent heat stabilizers
(see Control VIII and Control IX).
2. Employing diesters of the formula IXa type with organotin-
sulfur compounds does not adversely affect nor improve the
organotin-sulfur compounds' heat stabilizing efficiency (See Ex.
No. VIIIA, VIIIB, IXA and IXB).
Organotin carboxylates alone are extremely inefficient heat
stabilizers. However, it has been quite unexpectedly found that
the addition of an organotin carboxylate to a stabilizer contain-
ing an organotin-sulfur compound and a diester of the formula IXa
type produces a stabilizer composition which yields acceptable
heat stability. This is especially surprising in view of the
extremely poor efficiency of the organotin carboxylate.